Tetrakisazo-dyestuffs



United States Patent ice ilfj flii The amino-hydroxynaphthalene sulfonic acids must of course contain a, diazotizable, that is to say, a primary 2,762,793 amino group. This amino group may either be bound TErIRAmSAZ0 DYESTUFFS directly to the naphthalene nucleus or it may be present 5 in the form of a so-called external amino group, which Raymond F 3 Bimlmgel}! Switzerland, Ssign0r to Ciba is bound to the naphthalene nucleus by a suitable bridge hunted Basel swltzeflaud a SWISS firm member, for example, an NH-aryl radical or a hetero N0 Drawing Application September 27, 1954, ring fused on to the naphthalene ring. These coupling Serial 45 ,655 components contain a single sulfonic acid group bound 1 directly to the naphthalene nucleus, but they may also Claims Pmmty, apphcalwn gwltzefland October 9 1953 contain so-called external sulfonic acid groups which may 5 Claims (CL be present, for example, in the -NH-aryl radical referred to above. As an example of such a coupling component there may be mentioned 2-(4 '-aminophenyl- This invention provides new tetrakisazo-dyestufis which, 15 amino)-5-hydroxynaphthalene-7:3'-disulfonic acid. As like, for example, the dyestufi of the formula further examples of suitable amino-hydroxynaphthale-ne OH HOOC|7 OOOH H(|) correspond to the general formula in which R1 represents a diphenyl radical bound to the azo sulfonic acids there may be mentioned l-amino-S-hydroxylinkage in the 4- and 4'-positions and which contains in naphthalene-7-sulfonic acid and the compound of the 3- and 3 position each an -Oalkyl-COOH' group of formula low molecular weight or a -COOH group, and R2 and R3 represent the radical of hydroxynaphthalene sulfonic acids bound to the -N=NR1 group in a position I vicinal to the hydroxyl group and which each contain a HO3S 3 single sulfonic acid group bound to the naphthalene nucleus.

This invention also provides a process for making the 40 aforesaid tetrakisazo-dyestuifs, wherein a tetrazo-com- H0 pound of a diamino-disazo-dyestufi of the formula E u 1 M k d f d specia y va ua e tetra isazoyestui s are obtaine (3) R2 N=N R1 N:NR3 in the present process by using as starting materials in which R1 represents a diphenyl radical bound to the tetrazotized diamino-disazo-dyestuiis of the formula (4) 0H 1|; If Ht) H N NH;

SOaH azo linkage in the 4- and 4'-position and which contains in which X represents an O-CHz-COOH roup or a in 3- and 3'-position each an Oalkyl-COOH group COOH group and the NH2 groups are bound in 3- of low molecular weight or a carboxylic acid group, and positions to the naphthalene nuclei. These starting mate- R2 and R3 represent the radical of aminohydroxynaphrials are obtained by coupling tetrazotized 3:3-di-(carthalene sulfonic acids bound to the azo linkages in a boxymethoxy)-4:4-di-aminodiphenyl or tetrazotized 4:4- position vicinal to the hydroxyl group and which each diaminodiphenyl-3:3-dicarboxylic acid on both sides with contain a single sulfonic acid group bound tovthe naph- Z-amino-S-hydroxynaphthalene-7-sulfonic acid or 2- thalene radical, is coupled on both sides with 8-hydroXyamino-8-hydroxynaphthalene-6-sulfonic acid or with :1 duinoline. 6O mixture of these two components.

The disazo-dyestuffs of the Formula 3 are obtained by In order to obtain a unitary coupling in a position coupling on both sides a tetrazotized 4:4'-diarnino-divicinal to the hydroxyl group of the amino hydroxynaphphenyl compound substituted in the 3- and 3-positions thalene sulfonic acids these coupling components must by OalkylCOOH groups of low molecular weight usually be coupled with the tetrazotized diaminodiphenyl or COOH groups with amino-hydroxynaphthalene sulcompounds in an alkaline, medium, for example, a medium fonic acids of the kind defined above, it usually being of rendered alkaline with an alkali metal carbonate. More advantage to couple the tetrazo-compound on both sides over, it is of advantage to run a solution of the tetrazowith the same amino-hydroxynaphthalene sulfonic acid compound slowly into the alkaline solution of the couor at least with similar amine-hydroxynaphthalene sulpling component. This procedure is especially advantafonic acids. As diamines there come into consideration, geous for making the diaminodisazo-dyestuffs of the for example, 3:3-di-(carboxymethoxy) 4:4- diaminodi- Formula 4.

phenyl or 4:4'-diaminodiphenyl-3:3'-dicarboxylic acid. The diaminodisazo-dyestulfs of theFormula 3 are advantageously tetrazotized by the so-called indirect method by mixing, for example, a solution which contains the diamino-disazo-dyestuif in the form of an alkali salt and advantageously containing a small excess of free alkali and also the necessary quantity of alkali metal nitrite, with an excess of dilute hydrochloric acid.

The coupling of the tetrazo-disazo-compound with 8- hydroxyquinoline is advantageouslycarried out in an alkaline medium, for example, a medium rendered alkaline with an alkali bicarbonate or alkali carbonate, if desired, with the addition of a substance capable of assisting the coupling, such as pyridine or alcohol. It is also generally of advantage to couple the S-hydroxyquinoline in a finely divided state, for example, by precipitating it from a solution in hydrochloric acid by means of an alkali before or after mixing it with the tetrazo-disazo-compound.

The new tetrakisazo-dyestuffs correspond to the above Formula 2 and are suitable for dyeing a very wide variety of materials, for example, materials of animal origin such as wool, silk, or leather, but especially for dyeing or printing cellulosecontaining materials such as cotton, linen and staple fibers of regenerated cellulose. The dyestufis may be converted into complex metal compounds in substance, in the dyebath or on the fiber. The treatment with an agent yielding metal, for example an agent yielding copper, is advantageously carried out on the fiber or partially on the fiber and partially in the dyebath. If desired, there may be used the process of U. S. Patent 2,148,659 in which there are carried out in the same bath first the dyeing, and after the dyestufi has been practically completely absorbed, the treatment with the agent yielding metal. As agents yielding metal for the latter process there come into consideration those which are stable towards alkaline solutions, such as complex copper tartrates.

In some cases valuable dyeings can also be obtained by using the process in which a dyeing or print produced with the metal-free dyestuff is after-treated with an aqueous solution which contains a basic formaldehyde condensation product from a compound which contains at least once the atomic grouping or of a substance, for example cyanamide, which can easily be converted into such a compound, and which solution also contains a water-soluble, and especially a complex, copper compound. Such a process is described, for example, in British Patent No. 619,969.

The coppered dyeings obtainable in the manner described above with the new tetrakisazo-dyestuffs are distinguished by their very good fastness to light and washmg.

The following examples illustrate the invention, the parts being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

Example 1 27.2 parts of 4:4'-diaminodiphenyl-3:3'-dicarboxylic acid are tetrazotized in known manner. The tetrazo-compound is coupled by slowly introducing it dropwise at room temperature into a solution rendered alkaline with sodium carbonate of 512 parts of 2-amino-5-hydroxynaphthalene-7-sulfonic acid. The symmetrical disazodyestutf is precipitated by the addition of sodium chloride, filtered off and washed with a dilute solution of sodium chloride.

The disazo-dyestutf is then dissolved in 1000 parts of water at 80 C., 14.5 parts of sodium nitrite are added in the form of a 2N-solution, and the mixture is run at -5 C. into a solution of 60 parts by volume of hydrochloric acid of 30 per cent strength in 300 parts of water. By the addition of ice the temperature is maintained at 0-5 C. throughout. After stirring the mixture for several hours, the sparingly soluble tetrazo-compound is filtered off and again suspended in water. For the purpose of coupling, a solution of 29 parts of 8-hydroxyquinoline dissolved in 300 parts of water in the form of its semisulfate by the addition of sulfuric acid is added to the suspension of the tetrazo-compound, and by gradually throwing in sodium bicarbonate the coupling mixture is rendered weakly alkaline. The tetrakisazo-dyestuff precipitates in the form of a black precipitate. When dry it is a black powder having a bronze lustre, which dissolves in water with a blue coloration and dyes cellulose fibers by the single bath or 2-bath after-coppering process navy blue tints which are fast to washing and light.

By using for the first coupling, instead of 51.2 parts of 2 amino 5 hydroxynaphthalene 7 sulphonic acid, 83 parts of 2 (4' aminophenylamino) 5 hydroxynaphthalene-7:3-disulfonic acid and otherwise proceeding in the manner described in this example, a very similar dyestuff is obtained.

Example 2 27.2 parts of 4:4diaminodiphenyl 3:3 dicarboxylic acid are tetrazotized in the usual manner and coupled with 51.2 parts of 2-amino-8hydroxynaphthalene 6 sulfonic acid in a manner analogous to that described in Example 1. The further procedure is as described in Example 1, that is to say, the isolated disazo-dyestuff is further tetrazotized and the tet-razo-compound, after being isolated, is coupled with s-hydroxyquinoline. When dry the resulting tetrakisazo-dyestuff is a black powder having a bronze lustre, which dissolves in water with a dark grey-blue coloration and dyes cellulose fibers by the single bath or 2-bath after-coppering process grey to black tints which are fast to Washing and light.

By using for the first coupling, instead of 51.2 parts of 2 amino 8 hydroxynaphthalene 6 sulfonic acid, a mixture of 25.6 parts each of 2 amino 8 hydroxynaphthalene-G-sulfonic acid and 2-amino-5-hydroxynaphthalene-7-sulfonic acid and otherwise proceeding as described in Example 1, there is obtained a dyestulf having very similar properties which dyes cellulose fibers by the after-coppering process dull navy blue tints.

Example 3 33.2 parts of 4:4 diaminodiphenyl 3:3 diglycollic acid (3:3 di (carboxymethoxy) 4:4 diaminodiphenyl of the formula are dissolved in the form of the sodium salt and tetrazotized in known manner by the so-called indirect method. The tetrazo-compound is coupled by slowly introducing it dropwise at room temperature into a solution rendered alkaline with sodium carbonate of 51.2 parts of 2 amino 5 hydroxynaphthalene 7 sulfonic acid. The symmetrical disazo-dyestuff is precipitated by the addition of sodium chloride, filtered ofi and washed with a dilute solution of sodium chloride.

The disaZo-dyestufr' is then dissolved in 1000 parts of water at C., parts of sodium nitrite are added in the form of a 2 N-solution, and the mixture is run at 0-5 C. into a solution of 60 parts by volume of hydrochloric acid of 30 per cent strength in 300 parts of water.

By the addition of ice the temperature is maintained at 0-5 C. throughout. After stirring the mixture for several hours, the sparingly soluble tetrazo-compound is filtered oif and again suspended in water. For the purpose of coupling a solution of 29 parts of 8-hydroxyquinoline dissolved in 300 parts of water in the form of its semi-sulfate by the addition of sulfuric acid is added to cool to about 70 C., 2 parts of complex sodium copto the suspension of the tetrazo-compound, and by slowly per tartrate of approximately neutral reaction are then throwing in sodium bicarbonate the coupling mixture is added, coppering is carried on for /2 hour at about 80 rendered weakly alkaline. The tetrakisazo-dyestuif pre- C., and the dyeing is rinsed with cold water. If desired, cipitates in the form of a black precipitate. When dry it 5 the dyeing may be soaped by after-treatment with a soluis a black powder with a bronze lustre, which dissolves tion which contains 5 parts of soap and 2 parts of anin water with a blue coloration and dyes cellulose fibers hydrous sodium carbonate in 1000 parts by volume of by the single bath or 2-bath after-coppering process navy water. There is obtained a navy blue dyeing of good blue tints which are fast to light and washing. fastness to washing and light.

Further dyestuifs having similar properties are obtained What is claimed is: by using in this example, instead of Z-amino-S-hydroxy- 1. A tetrakisazo-dyestuif of the formula HOOC-'( flC(i))n1 (0CH2)-1-CO0H HO N=N-Rr-N=N-O j N=N-Rr-N=NQOH N N naphthalene-7-sulfonic acid, another amino-hydroxynaphin which R2 represents the radical of a hydroxynaphthalene sulfonic acid or a mixture of such sulfonic acids. thalene sulfonic acid bound to the N=N-diphenyl radi- Thus, there is obtained with 2-amino-8-hydroxynaphcal in a position vicinal to the hydroxyl group and conth'alene-6-sulfonic acid a dyestuff which dyes cellulose taining a single sulfonic acid group bound to the naphthafibers by the after-coppering dyeing process greenish black lene nucleus, and n represents a whole number of at the tints having an excellent fastness to light. most 2.

2. A tetrakisazo-dyestuff of the formula HOOC-(CHr-Oh-r (OCH2)n-iCOOH 0H I I H0 H0 N=N 03H Hols N=NOH N N Exam le 4 in which n represents a whole number of at the most p 2 and all the azo linkages are bound in fl-positions to the 100 parts of cotton are entered at C. into a dyenaphthalene nuclei. bath which contains in 4000 parts of water 3 parts of the 3. The tetrakisazo-dyestuif of the formula HOOC-HzC-O o-0H;-000H OH I I H0 H0 N=N SOaH HOxS N=N OH 4. The tetrakisazo-dyestuif of the formula I H O HO N=N N=N-G N= N=N N sour Hols N 5. The tetrakisazo-dyestuif of the formula HOOC-HzO-O O-CHzC-CO OH OH I I HO HO =NQHN S 03H H018 N HQN=N OH 1' N H088 0;H N

tetrakisazo-dyestufi obtained as described in the first and References Cited in the file of this patent second paragraphs of Example 1, and 2 parts of anhy- UNITED STATES PATENTS drous sodium carbonate. The temperature is raised to 90-95 C. in the course of 20 minutes, 40 parts of crys- 1,879,240 Hilger et a1. Sept. 27, 1932 talline sodium sulfate are added, and dyeing is continued 2,283,294 Straub et al May 19, 1942 for 30 minutes at 90-100 C. The bath is then allowed 2,507,754 Bossard et a1 May 16, 1950 

1. A TETRAKISAZO-DYESTUFF OF THE FORMULA 